Showing papers on "Noble metal published in 2013"

Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis

Abstract: Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe100-y-zCoyNizOx are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

Ni–Mo Nanopowders for Efficient Electrochemical Hydrogen Evolution

Abstract: Earth-abundant metals are attractive alternatives to the noble metal composite catalysts that are used in water electrolyzers based on proton-exchange membrane technology. Ni–Mo alloys have been previously developed for the hydrogen evolution reaction (HER), but synthesis methods to date have been limited to formation of catalyst coatings directly on a substrate. We report a method for generating unsupported nanopowders of Ni–Mo, which can be suspended in common solvents and cast onto arbitrary substrates. The mass-specific catalytic activity under alkaline conditions approaches that of the most active reported non-noble HER catalysts, and the coatings display good stability under alkaline conditions. We have also estimated turnover frequencies per surface atom at various overpotentials and conclude that the activity enhancement for Ni–Mo relative to pure Ni is due to a combination of increased surface area and increased fundamental catalytic activity.

All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures

Abstract: Noble metal nanoparticles are used for applications in optics, catalysis, sensing and others. Here the authors study the crystal structures of silver and gold-silver intermetallic nanoparticles stabilized by thiol ligand layers, helping to understand the relationship between their structure and properties.

Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction

Abstract: The efficient catalysis of the electrochemical reduction of carbon dioxide is an important industrial process, usually performed by noble metal catalysts. Here the authors report a metal-free carbon nanofibre-based catalyst operating with a negligible overpotential, high current density and long-term stability.

Hierarchically Porous Nitrogen-Doped Graphene–NiCo2O4 Hybrid Paper as an Advanced Electrocatalytic Water-Splitting Material

Abstract: In this work, we report a three-dimensional (3D) oxygen evolution reaction (OER) catalyst with hierarchical pores for water splitting. The remarkable features of well-developed in- and out-of-plane pores, 3D conductive networks, and N-doping have greatly promoted the transport in electrodes and assured high catalytic efficiency. The 3D hybrid paper of N-doped graphene–NiCo2O4 has shown a remarkable OER catalytic activity that was comparable to that of previously reported noble metal catalysts (IrO2). The catalytic process occurred with favorable kinetics and strong durability. The dual-active-site mechanism is responsible for the excellent performance of the hybrid catalyst; that is, the edges of NiCo2O4 and the N (O)–metal (Ni or Co) bonds are both active sites. This study affords a new strategy to achieve optimal performance in 3D catalysts, which may be extended to the preparation of other 3D hybrid materials for a broad range of technological applications.

A study on the mechanism for the interaction of light with noble metal-metal oxide semiconductor nanostructures for various photophysical applications

Abstract: Metal oxide semiconductors hold great promise for applications in energy conversion and storage, environmental remediation, optoelectronics, memory, light emission and other areas, but critical factors such as the high rate of charge-carrier recombination and limited light absorption have restricted more practical and viable applications. The remarkable ability of plasmonic noble metals to concentrate and scatter visible light has found a versatile potential in harvesting and converting solar energy. Plasmonic nanostructures of noble metals in combination with semiconductors offer a promising future for the next generation of energy needs. The overlap of the spectral range of the incident photon with absorbance wavelength of the semiconductor and the surface plasmon bands of the plasmonic metal provides a useful tool to predict the enhancement in optical and electrical properties of hybrid semiconductor-noble metal nanostructures. Here we make an attempt to comprehensively review the role of plasmonic noble metals in the enhanced functions for photocatalytic activity, photoenergy conversion in DSSCs, enhanced light emission and photochromatism. We mainly focus on the improvement of performance in TiO2 or ZnO in combination with noble metals on representative photophysical applications. The mechanism behind their interaction with light is discussed in detail in each section.

High-index faceted noble metal nanocrystals

Abstract: The formation of novel and complex structures with specific morphologies from nanocrystals via a direct assembly of atoms or ions remains challenging. In recent years, researchers have focused their attention on nanocrystals of noble metals and their controlled synthesis, characterization, and potential applications. Although the synthesis of various noble metal nanocrystals with different morphologies has been reported, most studies are limited to low-index facet-terminated nanocrystals. High-index facets, denoted by a set of Miller indices {hkl} with at least one index greater than unity, possess a high density of low-coordinated atoms, steps, edges, and kinks within these structures and serve as more active catalytic sites. With the potential for enhanced catalytic performance, researchers have used the insights from shape-controlled nanocrystal synthesis to construct noble metal nanocrystals bounded with high-index facets. Since the report of Pt tetrahexahedral nanocrystals, researchers have achieved ...

Efficient noble metal-free (electro)catalysis of water and alcohol oxidations by zinc-cobalt layered double hydroxide.

Abstract: Replacing rare and expensive noble metal catalysts with inexpensive and earth-abundant ones for various renewable energy-related chemical processes as well as for production of high value chemicals is one of the major goals of sustainable chemistry Herein we show that a bimetallic Zn–Co layered double hydroxide (Zn–Co–LDH) can serve as an efficient electrocatalyst and catalyst for water and alcohol oxidation, respectively In the electrochemical water oxidation, the material exhibits a lower overpotential, by ∼100 mV, than monometallic Co-based solid-state materials (eg, Co(OH)2 and Co3O4)-catalytic systems that were recently reported to be effective for this reaction Moreover, the material’s turnover frequency (TOF) per Co atoms is >10 times as high as those of the latter at the same applied potentials The Zn–Co–LDH also catalyzes oxidation of alcohols to the corresponding aldehydes or ketones at relatively low temperature, with moderate to high conversion and excellent selectivity

Screening of Catalysts for Hydrodeoxygenation of Phenol as a Model Compound for Bio-oil

Abstract: Four groups of catalysts have been tested for hydrodeoxygenation (HDO) of phenol as a model compound of bio-oil, including oxide catalysts, methanol synthesis catalysts, reduced noble metal catalysts, and reduced non-noble metal catalysts. In total, 23 different catalysts were tested at 100 bar H2 and 275 °C in a batch reactor. The experiments showed that none of the tested oxides or methanol synthesis catalysts had any significant activity for phenol HDO under the given conditions, which were linked to their inability to hydrogenate the aromatic ring of phenol. HDO of phenol over reduced metal catalysts could effectively be described by a kinetic model involving a two-step reaction in which phenol initially was hydrogenated to cyclohexanol and then subsequently deoxygenated to cyclohexane. Among reduced noble metal catalysts, ruthenium, palladium, and platinum were all found to be active, with activity decreasing in that order. Nickel was the only active non-noble metal catalyst. For nickel, the effect o...

Enhanced Catalytic Performance of Pt-Free Iron Phthalocyanine by Graphene Support for Efficient Oxygen Reduction Reaction

Abstract: It is commonly accepted that it is almost not possible to realize the large-scale practical application of fuel cells if the expensive noble metal-based electrocatalysts for oxygen reduction reactions (ORR) cannot be replaced by other low-cost, efficient, and stable ones. Herein, our studies demonstrate that iron phthalocyanine (FePc) supported on chemically reduced graphene through π–π interaction can act as a noble metal-free electrocatalyst with a comparable activity, long-term operation stability, and better tolerance to methanol crossover and CO poisoning compared with commercial Pt/C for ORR in alkaline media. The improved electrochemical activity and stability of FePc by graphene is mainly attributed to the inherent properties of graphene and the π-stacking interaction between FePc and planar aromatic structure of graphene. The as-prepared graphene–iron phthalocyanine (g-FePc) composite exhibits an efficient 4-electron pathway and can be used as a promising Pt-free ORR electrocatalyst.

Plasmonics in the ultraviolet with the poor metals Al, Ga, In, Sn, Tl, Pb, and Bi

Abstract: We discuss how the poor metals Al, Ga, In, Sn, Tl, Pb, and Bi can be used for plasmonics in the near to far ultraviolet (UV) range, similar to the noble metals Ag and Au in the visible (Vis) range. We first discuss the empirical dielectric functions of the poor metals, contrasting them with Ag and Au, and also fitting them to a Drude and multiple Lorentz oscillator form. Using Mie theory, we then compare the optical responses of spherical poor metal nanoparticles to noble metal ones. Finally, nanoparticle dimers are studied using a vectorial finite element method. We show how the poor metals exhibit large electric field enhancements in the UV, comparable to Au in the Vis, which makes them particularly attractive for sensing applications, such as surface enhanced Raman spectroscopy.

Highly Active, Nonprecious Metal Perovskite Electrocatalysts for Bifunctional Metal-Air Battery Electrodes.

Abstract: Perovskites are of great interest as replacements for precious metals and oxides used in bifunctional air electrodes involving the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, we report the synthesis and activity of a phase-pure nanocrystal perovskite catalyst that is highly active for the OER and ORR. The OER mass activity of LaNiO3, synthesized by the calcination of a rapidly dried nanoparticle dispersion and supported on nitrogen-doped carbon, is demonstrated to be nearly 3-fold that of 6 nm IrO2 and exhibits no hysteresis during oxygen evolution. Moreover, strong OER/ORR bifunctionality is shown by the low total overpotential (1.02 V) between the reactions, on par or better than that of noble metal catalysts such as Pt (1.16 V) and Ir (0.92 V). These results are examined in the context of surface hydroxylation, and a new OER cycle is proposed that unifies theory and the unique surface properties of LaNiO3.

Noble‐Metal‐Free NiS/C3N4 for Efficient Photocatalytic Hydrogen Evolution from Water

Abstract: A NiS/C3N4 photocatalyst containing earth-abundant elements only was constructed by means of a simple hydrothermal method. This photocatalyst shows efficient hydrogen evolution (48.2 μmol h−1) under visible light when using triethanolamine as a sacrificial reagent. The optimal loading of 1.1 wt % NiS on C3N4 as a cocatalyst can enhance the H2 production by about 250 times compared with the native C3N4. The highest apparent quantum efficiency of 1.9 % was recorded at 440 nm.

Ordered mesoporous Co3O4 spinels as stable, bifunctional, noble metal-free oxygen electrocatalysts

Abstract: We report the use of noble metal-free ordered mesoporous Co3O4 spinels (meso-Co3O4), templated from KIT-6 mesoporous silica, as highly active and stable bifunctional electrocatalysts for both oxygen evolution and reduction reactions (OER and ORR, respectively). The meso-Co3O4 nanostructures showed high activity for OER in an alkaline medium (0.1 M KOH), which makes them comparable to the most active Ir/C catalyst and better than Co3O4 nanoparticles (NPs) and the Pt/C catalyst. Furthermore, meso-Co3O4 exhibited enhanced stability, compared to Co3O4 NPs. The enhanced activity and stability of meso-Co3O4 over Co3O4 NPs could be attributed to its high surface area and structural stability of the gyroid network structure in the meso-Co3O4 catalysts. The meso-Co3O4 nanostructures also showed promising activity for ORR and exhibited a methanol-tolerance superior to the Pt/C catalyst. The total overpotential of meso-Co3O4 for OER (at 10 mA cm−2) and ORR (at −3 mA cm−2) was 1.034 V, which is on a par with noble metal-based catalysts. This work demonstrates that directing metal oxides into mesostructures is a promising means of preparing highly active, stable, bifunctional oxygen electrocatalysts that can potentially replace expensive noble metal-based catalysts. This design strategy can be extended to other reactions relevant to energy conversion and storage applications.

Defect-Mediated Growth of Noble-Metal (Ag, Pt, and Pd) Nanoparticles on TiO2 with Oxygen Vacancies for Photocatalytic Redox Reactions under Visible Light

Abstract: A synergistic strategy involving oxygen-vacancy generation and noble-metal deposition is developed to improve the photocatalytic performance of TiO2 under visible-light irradiation. Through a redox reaction between the reductive TiO2 with oxygen vacancies (TiO2-OV) and metal salt precursors, noble-metal nanoparticles (Ag, Pt, and Pd) are uniformly deposited on the defective TiO2-OV surface in the absence of any reducing agents or stabilizing ligands. The resulting M-TiO2-OV (M = Ag, Pt, and Pd) nanocomposites are used as visible-light-driven photocatalysts for selective oxidation of benzyl alcohol and reduction of heavy metal ions Cr(VI). The results show that the oxygen vacancy creation obviously enhances the visible-light absorption of semiconductor TiO2. Meanwhile, the noble-metal deposition can effectively improve charge-separation efficiency of TiO2-OV under visible-light irradiation, thereby enhancing the photoactivity. In particular, Pd-TiO2-OV, having the average Pd particle size of 2 nm, shows th...

Catalytically active single-atom niobium in graphitic layers

Abstract: Carbides of groups IV through VI (Ti, V and Cr groups) have long been proposed as substitutes for noble metal-based electrocatalysts in polymer electrolyte fuel cells. However, their catalytic activity has been extremely limited because of the low density and stability of catalytically active sites. Here we report the excellent performance of a niobium-carbon structure for catalysing the cathodic oxygen reduction reaction. A large number of single niobium atoms and ultra small clusters trapped in graphitic layers are directly identified using state-of-the-art aberration-corrected scanning transmission electron microscopy. This structure not only enhances the overall conductivity for accelerating the exchange of ions and electrons, but it suppresses the chemical/thermal coarsening of the active particles. Experimental results coupled with theory calculations reveal that the single niobium atoms incorporated within the graphitic layers produce a redistribution of d-band electrons and become surprisingly active for O2 adsorption and dissociation, and also exhibit high stability.

Base Metal Catalysts for Photochemical C–H Borylation That Utilize Metal–Metal Cooperativity

Abstract: Heterobimetallic Cu–Fe and Zn–Fe complexes catalyze C–H borylation, a transformation that previously required noble metal catalysts. The optimal catalyst, (IPr)Cu-FeCp(CO)2, exhibits efficient activity at 5 mol% loading under photochemical conditions, shows only minimal decrease in activity upon reuse, and is able to catalyze borylation of a variety of arene substrates. Stoichiometric reactivity studies are consistent with a proposed mechanism that exploits metal–metal cooperativity and showcases bimetallic versions of the classical organometallic processes, oxidative addition and reductive elimination.

Hydrogen evolution from Pt/Ru-coated p-type WSe2 photocathodes.

Abstract: Crystalline p-type WSe_2 has been grown by a chemical vapor transport method. After deposition of noble metal catalysts, p-WSe_2 photocathodes exhibited thermodynamically based photoelectrode energy-conversion efficiencies of >7% for the hydrogen evolution reaction under mildly acidic conditions, and were stable under cathodic conditions for at least 2 h in acidic as well as in alkaline electrolytes. The open circuit potentials of the photoelectrodes in contact with the H^(+)/H_2 redox couple were very close to the bulk recombination/diffusion limit predicted from the Shockley diode equation. Only crystals with a prevalence of surface step edges exhibited a shift in flat-band potential as the pH was varied. Spectral response data indicated effective minority-carrier diffusion lengths of ~1 μm, which limited the attainable photocurrent densities in the samples to ~15 mA cm^(–2) under 100 mW cm^(–2) of Air Mass 1.5G illumination.

Electrochemical Detection of Arsenic(III) Completely Free from Noble Metal: Fe3O4 Microspheres-Room Temperature Ionic Liquid Composite Showing Better Performance than Gold

Abstract: In recent decades, electrochemical detection of arsenic(III) has been undergoing revolutionary developments with higher sensitivity and lower detection limit. Despite great success, electrochemical detection of As(III) still depends heavily on noble metals (predominantly Au) in a strong acid condition, thus increasing the cost and hampering the widespread application. Here, we report a disposable platform completely free from noble metals for electrochemical detection of As(III) in drinking water under nearly neutral condition by square wave anodic stripping voltammetry. By combining the high adsorptivity of Fe3O4 microspheres toward As(III) and the advantages of room temperature ionic liquid (RTIL), the Fe3O4-RTIL composite modified screen-printed carbon electrode (SPCE) showed even better electrochemical performance than commonly used noble metals. Several ionic liquids with different viscosities and surface tensions were found to have a different effect on the voltammetric behavior toward As(III). Unde...

Seed-mediated growth of noble metal nanocrystals: crystal growth and shape control

Abstract: Controlled synthesis of noble metal nanocrystals has received enormous attention due to the ability of tailoring the properties of nanocrystals by tuning their shape, size, and composition. The seed-mediated growth method is one of the most reliable and versatile methods to control the shapes of noble metal nanocrystals. This feature article highlights recent strategies regarding shape-controlled synthesis of noble metal nanocrystals by the seed-mediated growth method, with the aim of introducing new strategies and offering new mechanistic insights into nanocrystal shape evolution. Critical parameters affecting the nucleation and growth of noble metal NCs are systemically introduced and analyzed. New developments of extended seed-mediated growth methods were also introduced. Finally, the perspectives of future research on the seed-mediated growth method are also discussed.

A facile one-step way to anchor noble metal (Au, Ag, Pd) nanoparticles on a reduced graphene oxide mat with catalytic activity for selective reduction of nitroaromatic compounds

Abstract: A facile, one-step clean strategy has been utilized for anchoring noble metal (Au, Ag, Pd) nanoparticles onto the flat surface of two-dimensional (2D) graphene oxide (GO) nanosheets. Without using any additional reductants, surfactants or protecting ligands, the deposition of metallic noble metal (Au, Ag, Pd) nanoparticles on the partially reduced graphene oxide (PRGO) mat has been realized by a simple redox reaction between the noble metal precursors and GO in an aqueous solution. The main size distributions of the Au, Ag and Pd particles are centered on 1–20 nm, 3–10 nm and 0.5–3 nm, respectively. The as-obtained Au, Ag and Pd–PRGO nanocomposites display superb catalytic activities for the selective reduction of nitroaromatic compounds into the corresponding amino compounds under ambient conditions. The rates of reduction follow the sequence, Pd–PRGO > Ag–PRGO > Au–PRGO, suggesting that the smallest noble metal particles size affords the highest catalytic activity. In addition, considering that the Au, Ag and Pd–PRGO nanocomposites still hold the abundant functional groups of the original GO, these noble metal–PRGO composites maintain the excellent hydrophilic nature of GO, which provides a flexible platform for the further fabrication of PRGO–metal-based multicomponent functional materials by a wet-chemistry approach.

A noble-metal-free system for photocatalytic hydrogen production from water.

Abstract: A series of heteroleptic copper(I) complexes with bidentate PP and NN chelate ligands was prepared and successfully applied as photosensitizers in the light-driven production of hydrogen, by using [Fe3(CO)12] as a water-reduction catalyst (WRC). These systems efficiently reduces protons from water/THF/triethylamine mixtures, in which the amine serves as a sacrificial electron donor (SR). Turnover numbers (for H) up to 1330 were obtained with these fully noble-metal-free systems. The new complexes were electrochemically and photophysically characterized. They exhibited a correlation between the lifetimes of the MLCT excited state and their efficiency as photosensitizers in proton-reduction systems. Within these experiments, considerably long excited-state lifetimes of up to 54 μs were observed. Quenching studies with the SR, in the presence and absence of the WRC, showed that intramolecular deactivation was more efficient in the former case, thus suggesting the predominance of an oxidative quenching pathway.